JP2011505486A - High water content silicone hydrogel - Google Patents

Abstract

Silicone hydrogels formed from a hydrated polymerization product of a monomer mixture comprising (a) a major amount of a non-silicone-containing hydrophilic monomer; and (b) a minor amount of a silicone-containing monomer, wherein the hydrogel has a water content of greater than 50 weight percent are disclosed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to high water content silicone hydrogel materials.

Description of Related Art Hydrogels are a desirable class of materials for contact lenses. Hydrogels are hydrated crosslinked polymer systems that contain water in an equilibrium state. Hydrogel lenses provide a relatively high oxygen permeability coefficient and desirable biocompatibility and comfort.

  The oxygen transmission coefficient (Dk) is one important factor in the design of contact lenses to maintain the eye health of contact lens wearers. For example, contact lenses must be able to reach a sufficient amount of oxygen for long-term corneal health. Contact lenses must also allow oxygen to reach the cornea from ambient air. This is because the cornea does not receive oxygen from the blood supply like other tissues. Since “soft” contact lenses follow the shape close to the shape of the eye, oxygen cannot easily circumvent the lens. For this reason, soft contact lenses must be able to diffuse oxygen through the lens and reach the cornea.

  Another ophthalmic compliance requirement for soft contact lenses is that the lens must not adhere strongly to the eye. Obviously, the consumer must be able to easily remove the lens from the eye for disinfection, cleaning or disposal. However, the lens must also be able to move over the eye to promote tear flow between the lens and the eye. The tear flow between the lens and the eye can carry debris, such as foreign particles or dead epithelial cells, from under the lens, and finally from the tears. Thus, the contact lens should not adhere so strongly to the eye that sufficient movement of the lens over the eye is suppressed.

  In order to balance the requirements of ophthalmic compatibility and consumer comfort in the design of everyday wear soft contact lenses, it is composed of a copolymer of hydrophilic monomers such as 2-hydroxyethyl methacrylate (HEMA), N-vinyl pyrrolidone, Then, a lathe cutting method, spin casting method, cast molding method or a combination thereof, and then a swelling treatment in physiological saline and / or phosphate buffer solution are performed to obtain a lens having a water content of about 20 to about 80% by mass. A conventional hydrogel contact lens with high water content, prepared by obtaining, has been developed. These hydrophilic polymers move well on the eye and provide sufficient oxygen permeability for everyday wear.

  Prior art high water content silicone-containing hydrophilic soft contact lenses tend to have reduced or low oxygen permeability. For example, a silicone hydrogel contact lens available under the trade name Focus Night & Day (available from CIBA Vision Corporation) has a moisture content of about 24% and a Dk of about 140 Barrer. is there. Another silicone hydrogel contact lens available under the name O2 Optix (available from CIBA Vision Corporation) has a moisture content of about 33% and a Dk of about 110 Barrer. Another silicone hydrogel contact lens available under the trade name (Acuvue Oasys) (available from Johnson & Johnson) has a moisture content of about 38% and a Dk of about 105 Barrer. Another silicone hydrogel contact lens available under the trade name Vision (available from Bausch & Lomb) has a moisture content of about 36% and a Dk of about 100 Barrer. Another silicone hydrogel contact lens available under the trade name (available from Johnson & Johnson) has a moisture content of about 46 to about 47. In comparison, the non-silicone hydrogel contact lens available under the trade name Acuvue 2 (available from Johnson & Johnson) has a moisture content of about 58%. Yes, Dk is about 25 Barrer.

  U.S. Pat. No. 5,260,000 casts a monomer mixture containing a major amount of silicone-containing monomer, hydrophilic monomer and n-nonanol or n-hexanol as a diluent and then extracted with isopropanol. Disclosed are methods for preparing silicone hydrogel contact lenses that remove residual diluent and unreacted monomers and oligomers. However, the problems associated with producing low-cost lenses from silicone hydrogels include the need for a solvent extraction step in the production process to remove unreacted silicone, as well as wettable, lubricious, and low-contamination surfaces. It is required to perform a post-polymerization surface modification step to provide

U.S. Pat. No. 7,268,198 (the '198 patent) includes N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-ethylformamide, N-vinylformamide, A silicone hydrogel that is a hydrated polymerization product of a monomer mixture comprising a hydrophilic monomer selected from the group consisting of N-vinylpyrrolidone and mixtures thereof and a polysiloxane-containing monomer, wherein the oxygen permeability coefficient is at least about 120 barrers. And a silicone hydrogel having an elastic modulus of 40 to 57 g / mm ² is disclosed. However, each example of the '198 patent forms a silicone hydrogel having a moisture content of 19.2% to 35.3%.

  It would be desirable to provide improved high water content silicone hydrogels.

SUMMARY OF THE INVENTION According to one embodiment of the present invention, a hydrous polymer formed from a hydrated polymerization product of a monomer mixture comprising (a) a greater amount of non-silicone-containing hydrophilic monomer and (b) a lesser amount of silicone-containing monomer. A silicone hydrogel is provided having a rate greater than 50% by weight.

  According to a second embodiment of the present invention, the water content is formed from a hydrated polymerization product of a monomer mixture comprising (a) a greater amount of non-silicone-containing hydrophilic monomer and (b) a smaller amount of silicone-containing monomer. Silicone hydrogels are provided that are greater than 70% by weight and have an oxygen permeability coefficient of about 30 to about 70 Barrer.

  According to a second embodiment of the present invention, the water content is formed from a hydrated polymerization product of a monomer mixture comprising (a) a greater amount of non-silicone-containing hydrophilic monomer and (b) a smaller amount of silicone-containing monomer. Contact lenses comprising a silicone hydrogel greater than 50% by weight are provided.

  In the preparation of silicone hydrogels, the use of a lower amount of silicone-containing monomer relative to a base material containing a higher amount of non-silicone-containing hydrophilic monomer allows the silicone-containing monomer to have properties of the bulk material (eg, oxygen permeability, Modulus, elastic modulus, etc.) and its surface properties (eg, wettability, lubricity, etc.) will have no substantial effect. Furthermore, the silicone hydrogel of the present invention advantageously forms with the desired hydrophilic surface and high moisture content without having to perform a solvent extraction step and a post-polymerization surface treatment step while having suitable oxygen permeation properties. be able to. In this way, silicone hydrogels can be manufactured in a relatively efficient process and on a low cost platform.

Detailed Description of the Preferred Embodiments The present invention is formed from a hydrated polymerization product of a monomer mixture comprising (a) a greater amount of non-silicone-containing hydrophilic monomer and (b) a lesser amount of silicone-containing monomer, wherein the water content is More than 50% by weight of silicone hydrogel. As used herein, the term “monomer” refers to relatively low molecular weight compounds that can be polymerized by radical polymerization, as well as terms such as “prepolymer”, “macromonomer”, and more. Refers to a high molecular weight compound.

  Suitable non-silicone-containing hydrophilic monomers include, but are not limited to, unsaturated carboxylic acids such as (meth) acrylic acid, (meth) acryl substituted alcohols, vinyl lactams, (meth) acrylamides and the like. As used herein, the term “(meth)” refers to an optionally present methyl substituent. Thus, terms such as “(meth) acrylate” refer to either methacrylate or acrylate, and “(meth) acrylamide” refers to either methacrylamide or acrylamide. Specific examples of non-silicone-containing hydrophilic monomers include methacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethylacrylamide, glyceryl methacrylate, N- (2-hydroxyethyl) methacrylamide. , N-methacryloylglycine and (2-hydroxy-3-methacryloylpropyl) -4-methoxyphenyl ether. Preferred monomers include N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone (NVP), 2-hydroxyethyl methacrylate (HEMA) and mixtures thereof.

  Non-silicone-containing hydrophilic monomers are present in higher amounts in the monomer mixture (the term is intended to include a mixture of hydrophilic monomers), ie, at least 50 parts by weight of the total components in the monomer mixture. Included in quantity. In one embodiment, the non-silicone-containing hydrophilic monomer is present in the monomer mixture in the range of about 50 to about 95 parts by weight of the total monomer mixture component, with about 60 to about 90 parts by weight being particularly preferred. In a preferred embodiment, the monomer mixture comprises at least about 60 parts by weight, more preferably at least about 80 parts by weight of the non-silicone-containing hydrophilic monomer component, such that the resulting silicone hydrogel is used as a silicone hydrogel material. Therefore, it is remarkably hydrophilic and wettable.

  The silicone-containing monomer can be any polymerizable silicone-containing monomer. The monomer may be added as a monomer or prepolymer to the monomer mixture to obtain a molded article. For this reason, it is understood that the terms “silicone-containing monomer” and “hydrophilic monomer” include prepolymers. For example, in one embodiment, the silicone-containing monomer can be a nonionic silicone-containing monomer. Applicable silicone-containing monomer units for use in the formation of silicone hydrogels are well known in the art and numerous examples are described, for example, in U.S. Pat. No. 4,136,250, U.S. Pat. No. 153,641, No. 4,740,533, No. 5,034,461, No. 5,070,215, No. 5,260,000 No. 5,310,779 and US Pat. No. 5,358,995.

Typical examples of applicable silicone-containing monomer units include bulky siloxanyl monomers represented by the structure of the following formula I.

  In the above formula, X is —O— or —NR ″ —, R ″ is hydrogen, methyl or ethyl, each R ′ is independently hydrogen or methyl, and each R is independently a lower alkyl group, phenyl Group or group of the following formula

であり、ここで、各Ｒ'''は独立に低級アルキル基又はフェニル基であり、ｈは１〜１０である。

Wherein each R ′ ″ is independently a lower alkyl group or a phenyl group, and h is 1-10.

  Examples of bulky monomers are 3-methacryloyloxypropyltris (trimethylsiloxy) silane or tris (trimethylsiloxy) silylpropyl methacrylate, often referred to as TRIS, or tris (trimethylsiloxy) silylpropylvinylcarbamate, often referred to as TRIS-VC, pentamethyldi Siloxanylmethyl methacrylate, phenyltetramethyldisiloxanylethyl acetate and methyldi (trimethylsiloxy) methacryloxymethylsilane and the like and mixtures thereof. In one embodiment, the silicone-containing monomer is a tris (trialkylsiloxy) silylalkyl methacrylate-containing monomer, such as a tris (trimethylsiloxy) silylpropyl methacrylate-containing monomer.

  Such bulky monomers can be copolymerized with silicone macromonomers, which are, for example, poly (organosiloxanes) capped with unsaturated groups at two or more ends of the molecule. U.S. Pat. No. 4,153,641 discloses various unsaturated groups such as, for example, acryloyloxy or methacryloyloxy groups.

Another class of representative silicone-containing monomers includes, but is not limited to, silicone-containing vinyl carbonate or vinyl carbamate monomers such as 1,3-bis [4-vinyloxycarbonyloxy) but-1-yl]. Tetramethyldisiloxane, 3- (trimethylsilyl) propyl vinyl carbonate, 3- (vinyloxycarbonylthio) propyl [tris (trimethylsiloxy) silane], 3- [tris (trimethylsiloxy) silyl] propyl vinylcarbamate, 3- [tris (Trimethylsiloxy) silyl] propylallylcarbamate, 3- [tris (trimethylsiloxy) silyl] propyl vinyl carbonate, t-butyldimethylsiloxyethyl vinyl carbonate, trimethylsilylethyl vinyl carbonate Boneto, trimethylsilylmethyl vinyl carbonate, V ₂ D ₂₅ of the following general formula

など及びそれらの混合物が挙げられる。

And mixtures thereof.

Another class of silicone-containing monomers includes polyurethane-polysiloxane macromonomers (sometimes referred to as prepolymers), which can have hard-soft-hard blocks similar to traditional urethane elastomers. The silicone-containing monomer can be endcapped with a hydrophilic monomer such as 2-hydroxyethyl methacrylate (HEMA). Examples of such silicone urethanes are disclosed in various documents including International Publication No. WO 96/31792. International Publication No. WO 96/31792 discloses examples of such monomers, the entire contents of which are incorporated herein by reference. Representative examples of silicone urethane monomers are represented by Formulas II and III.
E ( ^* D ^* A ^* D ^* G) _a ^* D ^* A ^* D ^* E '(II) or E ( ^* D ^* G ^* D ^* A) _a ^* D ^* A ^* D ^* E' (III)
D is independently an alkyl divalent group, an alkylcycloalkyl divalent group, a cycloalkyl divalent group, an aryl divalent group or an alkylaryl divalent group, having from 6 to about 30 carbon atoms;
G is independently an alkyl divalent group, a cycloalkyl divalent group, an alkylcycloalkyl divalent group, an aryl divalent group or an alkylaryl divalent group, having from 1 to about 40 carbon atoms, and Can contain ether, thio or amine linkages in the main chain;
* Is a urethane or ureido bond group,
a is at least 1,
A is independently a divalent polymer group of formula IV;

各Ｒ^Sは独立に、１〜約１０個の炭素原子を有する、アルキル基又はフルオロ置換アルキル基であり、それは炭素原子の間にエーテル結合を含むことができ、
ｍ’は少なくとも１であり、ｐは約４００〜約１０，０００の部分分子量を提供する数であり、
各Ｅ及びＥ’は独立に式Ｖにより表される重合性不飽和有機基であり、

Each R ^S is independently an alkyl or fluoro-substituted alkyl group having from 1 to about 10 carbon atoms, which can include an ether linkage between the carbon atoms;
m ′ is at least 1 and p is a number providing a partial molecular weight of about 400 to about 10,000;
Each E and E ′ is independently a polymerizable unsaturated organic group represented by Formula V;

In the above formula, R ³ is hydrogen or methyl,
R ⁴ is hydrogen, an alkyl group having 1 to 6 carbon atoms, or a —CO—Y—R ⁶ group, where Y is —O—, —S— or —NH—;
R ⁵ is a divalent alkylene group having 1 to about 10 carbon atoms;
R ⁶ is an alkyl group having 1 to about 12 carbon atoms;
X is —CO— or —OCO—.
Z is —O— or —NH—.
Ar is an aromatic group having from about 6 to about 30 carbon atoms;
w is 0 to 6, x is 0 or 1, y is 0 or 1, and z is 0 or 1.

A preferred silicone-containing urethane monomer is represented by Formula VI below.

Wherein m is at least 1, preferably 3 or 4, a is at least 1, preferably 1, and p is a number providing a partial molecular weight of about 400 to about 10,000. , Preferably at least about 30 and R ⁷ is a divalent group of the diisocyanate after removal of the isocyanate group, for example, a divalent group of isophorone diisocyanate, and each E ″ is the following group:

In another embodiment, the silicone-containing monomer is a cationic silicone-containing monomer. Representative examples of applicable cationic silicon-containing monomer units include cationic monomers of the following formula VII.

Each L is a urethane independently, carbonates, carbamates, carboxyl ureidos, sulfonyl, straight or branched C ₁ -C ₃₀ alkyl group, a linear or branched C ₁ -C ₃₀ fluoroalkyl group, ester-containing group, ether-containing group, poly ether-containing group, an ureido group, an amide group, an amine group, a substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkylalkyl group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkenyl group, a substituted or unsubstituted C ₅ -C ₃₀ aryl group, a substituted or unsubstituted C ₅ -C ₃₀ arylalkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl aryl group, a substituted or unsubstituted C ₃ -C ₃₀ heterocyclic group, a substituted or unsubstituted C ₄ -C ₃₀ Heteroshikuro May be an alkyl group, substituted or unsubstituted C ₆ -C ₃₀ heteroarylalkyl group, a C ₅ -C ₃₀ fluoroaryl group or hydroxyl substituted alkyl ether and combinations thereof.

X ⁻ is at least a monovalent charged counter ion. Examples of monovalent charged counter ions include Cl ⁻ , Br ⁻ , I ⁻ , CF ₃ CO ₂ ⁻ , CH ₃ CO ₂ ⁻ , HCO ₃ ⁻ , CH ₃ SO ₄ ⁻ , p-toluenesulfonate, HSO ₄ ⁻ , A group consisting of H ₂ PO ₄ ⁻ , NO ₃ ⁻ and CH ₃ CH (OH) CO ₂ ^— may be mentioned. Examples of divalent charged counter ions include SO ₄ ²⁻ , CO ₃ ²⁻ , and HPO ₄ ²⁻ . Other charged counter ions will be apparent to those skilled in the art. It should be understood that residual amounts of counterions may be present in the hydrated product. Therefore, the use of toxic counterions should be avoided. Similarly, it should be understood that for a monovalent charged counterion, the ratio of counterion to quaternary siloxanyl will be 1: 1. A more multivalent negatively charged counterion will have a different ratio based on the total charge of the counterion.

R ₁ and R ₂ are each independently hydrogen, linear or branched C ₁ -C ₃₀ alkyl group, linear or branched C ₁ -C ₃₀ fluoroalkyl group, C ₁ -C ₂₀ ester group, ether-containing group, poly ether-containing group, an ureido group, an amide group, an amine group, a substituted or unsubstituted C ₁ -C ₃₀ alkoxy group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkylalkyl group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkenyl group, a substituted or unsubstituted C ₅ -C ₃₀ aryl group, a substituted or unsubstituted C ₅ -C ₃₀ arylalkyl group, a substituted or unsubstituted C ₅ -C ₃₀ heteroaryl aryl group, a substituted or unsubstituted C ₃ -C ₃₀ heterocyclic group, a substituted or unsubstituted C ₄ -C ₃₀ heterocyclylalkyl crawl alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ hetero Arylalkyl group, a fluorine group, a C ₅ -C ₃₀ fluoroaryl group, or a hydroxyl group, and,
V is independently a polymerizable ethylenically unsaturated organic group.

Preferred monomers of formula VII are shown below in formula VIII.

Wherein each R ₁ is the same, —OSi (CH ₃ ) ₃ , R ₂ is methyl, L ₁ is an alkylamide, and L ₂ is an alkyl having 2 or 3 carbon atoms. An amide or ester, wherein L ₂ is bonded to a polymerizable vinyl group, R ₃ is methyl, R ₄ is H, and X ⁻ is Br ⁻ or Cl ⁻ .

及び

A more preferred structure has the following structural formulas IX-XIII.

as well as

A schematic diagram of a synthesis method for producing a cationic silicone-containing monomer as disclosed above is provided below.

Another class of examples of applicable cationic silicone-containing monomer units for use herein include cationic monomers of the following formula XIV.

In the above formula, can also be or different that each L is the same and is as defined above for L in formula VII, X ^- is X in formula VII ^- at least monovalent as defined above for R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently as defined for R ₁ in formula VII, and V is independent A polymerizable ethylenically unsaturated organic group, and n is an integer from 1 to about 300.

Preferred monomers of formula XIV are shown below in formulas XV-XIX.

A schematic diagram of a synthetic method for preparing a cationic silicone-containing monomer of formula XIV is provided below.

Another class of examples of applicable cationic silicone-containing monomer units for use herein include cationic monomers of formula XX below.

Wherein x is 0 to 1000, y is 1 to 300, each L can be the same or different, and is as defined above for L of formula VII, X ⁻ Is at least a monovalent charged counterion as defined above for X ⁻ of formula VII, wherein R ₁ , R ₁₃ and R ₁₄ are each independently as defined for R ₁ of formula VII, and A is A polymerizable vinyl moiety.

Preferred cationic random copolymers of formula XX are shown below in formula XXI.

  In the above formula, x is 0 to 1000, and y is 1 to 300.

A schematic diagram of a synthetic method for preparing cationic silicone-containing random copolymers of Formulas XX and XXI is provided below.

Another class of applicable cationic materials for use herein includes cationic random copolymers of formula XXII below.

Wherein x is 0 to 1000, y is 1 to 300, each R ₁₅ and R ₁₆ can be the same or different, and as defined above for R ₁ of formula VII Wherein R ₁₇ is independently one or more of the following formulas XXIII and XXIV:

as well as

In the above formula, L is also can or different be the same, and are as defined above for L in formula VII, X ^- is of formula VII X ^- for at least one monovalent as defined above A charged counterion, R ₁₈ can be the same or different and can be a group as defined above for R ₁ of formula VII, wherein R ₁₉ is independently hydrogen or methyl. .

  Provided below is a schematic diagram of a synthetic method for preparing cationic silicone-containing random copolymers such as poly (dimethylsiloxane) having pendant polymerizable cationic groups disclosed herein.

  Another synthetic scheme for producing poly (dimethylsiloxane) having pendant cationic groups and pendant polymerizable cationic groups is provided below.

  Yet another synthetic scheme for preparing poly (dimethylsiloxane) having pendant polymerizable groups and pendant cationic groups is provided below.

  Representative examples of urethanes for use herein include secondary amines attached to carboxyl groups that can be attached to additional groups such as, for example, alkyl. Similarly, secondary amines may be attached to additional groups such as alkyl.

  Representative examples of carbonates for use herein include, for example, alkyl carbonates, aryl carbonates, and the like.

  Representative examples of carbamate groups for use herein include, for example, alkyl carbamates, aryl carbamates, and the like.

  Representative examples of carboxyl ureido for use herein include, for example, alkyl carboxyl ureido, aryl carboxyl ureido and the like.

  Representative examples of sulfonyls for use herein include, for example, alkylsulfonyl, arylsulfonyl, and the like.

  Representative examples of alkyl groups for use herein include, for example, straight or branched hydrocarbon chains containing 1 to about 18 carbon atoms and hydrogen atoms in the rest of the molecule, Those containing or not containing saturation include, for example, methyl, ethyl, n-propyl, 1-methylethyl (or isopropyl), n-butyl, n-pentyl and the like.

Representative examples of fluoroalkyl groups for use herein include, for example, straight or branched alkyl groups as defined above having one or more fluorine atoms bonded to a carbon atom, For example, —CF ₃ , —CF ₂ CF ₃ , —CH ₂ CF ₃ , CH ₂ CF ₂ H, —CF ₂ H and the like can be mentioned.

  Representative examples of ester groups for use herein include, for example, carboxylic acid esters having 1 to 20 carbon atoms.

Representative examples of ether or polyether containing groups for use herein include, for example, alkyl ethers, cycloalkyl ethers, cycloalkyl alkyl ethers, cycloalkenyl ethers, aryl ethers, arylalkyl ethers, where Wherein the alkyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, aryl and arylalkyl groups are as defined herein, eg, alkylene oxide, poly (alkylene oxide), eg, ethylene oxide, propylene Oxides, butylene oxide, poly (ethylene oxide), poly (ethylene glycol), poly (propylene oxide), poly (butylene oxide) and mixtures or copolymers thereof, general formula -R ₂₀ OR _{21 wherein} R ₂₀ is a bond, an alkyl, cycloalkyl or aryl group as defined herein, and R ₂₁ is an alkyl, cycloalkyl or aryl as defined herein. For example, in the case of L as defined in formula VII, the ether-containing group is —CH ₂ CH ₂ OC ₆ H ₄ or —CH ₂ CH ₂ OC can be a ₂ H _4, or, in the case of R ₁ and R ₂ as defined in formula VII, ether-containing group is -CH ₂ CH ₂ OC ₆ H ₅ or -CH ₂ CH ₂ OC ₂ H ₅ or the like.

Representative examples of amide groups for use herein include, for example, the general formula —R ₂₃ C (O) NR ₂₄ R ₂₅ , wherein R ₂₃ , R ₂₄ and R ₂₅ are independently C _1- A C ₃₀ hydrocarbon group, for example, R ₂₃ is an alkylene group, an arylene group or a cycloalkylene group as defined herein; R ₂₄ and R ₂₅ are an alkyl group, an aryl group and a cycloalkyl group; And amides).

Representative examples of amine groups for use herein include, for example, the general formula —R ₂₆ NR ₂₇ R ₂₈ , wherein R ₂₆ is a C ₂ -C ₃₀ alkylene as defined herein. , Arylene or cycloalkylene, and R ₂₇ and R ₂₈ are each independently a C _{1 to} C ₃₀ hydrocarbon group, and can be, for example, an alkyl group, an aryl group, or a cycloalkyl group). .

  Representative examples of ureido groups for use herein include, for example, ureido groups having one or more substituted or unsubstituted ureido. The ureido group is preferably a ureido group having 1 to 12 carbon atoms. Examples of the substituent include an alkyl group and an aryl group. Examples of ureido groups include 3-methylureido, 3,3-dimethylureido and 3-phenylureido.

Representative examples of alkoxy groups for use herein include, for example, an alkyl group as defined above attached to the remainder of the molecule through an oxygen bond, ie, the general formula —OR _{29 wherein} R ₂₉ is alkyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, aryl or arylalkyl as defined above, eg, —OCH ₃ , —OC ₂ H ₅ or the like -OC ₆ H ₅ and the like.

  Representative examples of cycloalkyl groups for use herein include, for example, substituted or unsubstituted non-aromatic mono- or polycyclic systems of about 3 to about 18 carbon atoms, such as cyclopropyl , Cyclobutyl, cyclopentyl, cyclohexyl, perhydronaphthyl, adamantyl and norbornyl groups, bridged cyclic groups or spiro bicyclic groups such as spiro- (4,4) -non-2-yl, optionally Those containing one or more heteroatoms, such as O and N, are included.

  Representative examples of cycloalkylalkyl groups for use herein include, for example, substituted or unsubstituted ring-containing groups containing about 3 to about 18 carbon atoms bonded directly to the alkyl group. The alkyl group is bonded to the main structure of the monomer at any carbon position of the alkyl group, resulting in the formation of a stable structure, such as cyclopropylmethyl, cyclobutylethyl, cyclopentylethyl, etc. The above rings optionally include one or more heteroatoms, such as O and N.

  Representative examples of cycloalkenyl groups for use herein include, for example, substituted or unsubstituted ring containing from about 3 to about 18 carbon atoms having at least one carbon-carbon double bond Groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and the like, wherein the ring optionally includes one or more heteroatoms, such as O and N.

  Representative examples of aryl groups for use herein include, for example, substituted or unsubstituted monocyclic aromatic or polycyclic aromatic groups containing about 5 to about 25 carbon atoms, such as phenyl. , Naphthyl, tetrahydronaphthyl, indenyl, biphenyl, and the like, optionally containing one or more heteroatoms such as O and N.

Representative examples of arylalkyl groups for use herein include, for example, a substituted or unsubstituted aryl group as described above directly attached to an alkyl group as defined above, for example,- CH ₂ C ₆ H ₅ , —C ₂ H ₅ C ₆ H _5, etc., where the aryl group can optionally contain one or more heteroatoms such as O and N.

  Representative examples of fluoroaryl groups for use herein include, for example, aryl groups having one or more fluorine atoms bonded to an aryl group as described above.

  Representative examples of heterocyclic groups for use herein include, for example, 3 to about 15 membered substituted or unsubstituted stable ring groups comprising carbon atoms and 1 to 5 heteroatoms. The heteroatoms are, for example, nitrogen, phosphorus, oxygen, sulfur and mixtures thereof. Heterocyclic groups suitable for use herein can be monocyclic, bicyclic or tricyclic systems, which ring systems can include fused, bridged or spiro ring systems, and are among the heterocyclic groups. The nitrogen, phosphorus, carbon, oxygen, or sulfur atoms of may be optionally oxidized to various oxidation states. Further, the nitrogen may optionally be quaternized and the ring group may be partially or fully saturated (ie, heteroaromatic or heteroarylaromatic). Examples of such heterocyclic groups include, but are not limited to, azetidinyl, acridinyl, benzodioxolyl, benzodioxanyl, benzofurnyl, carbazolyl, cinolinyl, dioxolanyl, indolizinyl, naphthyridinyl, perhydroazepinyl , Phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pyridyl, pteridinyl, purinyl, quinazolinyl, quinoxalinyl, quinolinyl, isoquinolinyl, tetrazolyl, imidazolyl, tetrahydroisouinolyl, piperidinyl, piperazinyl, oxo Piperidinyl, 2-oxopyrrolidinyl, 2-oxoazepinyl, azepinyl, pyrrolyl, 4-piperidonyl, pyrrolidinyl, pyrazinyl, pyrimidinyl, Pyridazinyl, oxazolyl, oxazolinyl, oxasolidinyl, triazolyl, indanyl, isoxazolyl, isoxazolidinyl, morpholinyl, thiazolyl, thiazolinyl, thiazolidinyl, isothiazolyl, quinuclidinyl, isothiazolidinyl, indolyl, indolyl, indolyl , Octahydroindolyl, octahydroisoindolyl, quinolyl, isoquinolyl, decahydroisoquinolyl, benzimidazolyl, thiadiazolyl, benzopyranyl, benzothiazolyl, benzoxazolyl, furyl, tetrahydrofurtyl, tetrahydropyranyl, thienyl , Benzothienyl, thiamorpholinyl, thiamorpholinyl sulfoxide, thiamorpholinyl sulfone , Dioxaphosphoranyl, oxadiazolyl, chromanyl, isochromanyl and the like and mixtures thereof.

  Representative examples of heteroaryl groups for use herein include, for example, substituted or unsubstituted heterocyclic groups as defined above. The heteroaryl ring radical may be attached to the main structure at any heteroatom or carbon atom that results in the formation of a stable structure.

  Representative examples of heteroarylalkyl groups for use herein include, for example, a substituted or unsubstituted heteroaryl ring group as defined above directly bonded to an alkyl group as defined above. Is mentioned. A heteroarylalkyl group may be attached to the main structure at any carbon atom in the alkyl group that results in the formation of a stable structure.

  Representative examples of heterocyclo groups for use herein include, for example, substituted or unsubstituted heterocyclic groups as defined above. The heterocyclo ring group may be attached to the main structure at any heteroatom or carbon atom that results in the formation of a stable structure.

  Representative examples of heterocycloalkyl groups for use herein include, for example, substituted or unsubstituted heterocyclic groups as described above directly bonded to an alkyl group as described above. The heterocycloalkyl group may be attached to the main structure at any carbon atom in the alkyl group that will form a stable structure.

  Representative examples of the “polymerizable ethylenically unsaturated organic group” include, for example, a (meth) acrylate-containing group, a (meth) acrylamide-containing group, a vinyl carbonate-containing group, a vinyl carbamate-containing group, and a styrene-containing group. It is done. In one embodiment, the polymerizable ethylenically unsaturated organic group has the general formula

(In the above formula, R ₃₀ is independently hydrogen, fluorine, an alkyl group having 1 to 6 carbon atoms, or —CO—Y—R ₃₂ group, where Y is —O—, —S. -Or -NH-, R ₃₂ is a divalent alkylene group having from 1 to about 10 carbon atoms, and R ₃₁ is hydrogen, fluorine or methyl.

“Substituted alkyl”, “substituted alkoxy”, “substituted cycloalkyl”, “substituted cycloalkylalkyl”, “substituted cycloalkenyl”, “substituted arylalkyl”, “substituted aryl”, “substituted heterocyclic group”, “substituted” The substituents in the “heteroaryl ring”, “substituted heteroarylalkyl”, “substituted heterocycloalkyl ring”, “substituted cyclic ring” and “substituted carboxylic acid derivative” may be the same or different, And one or more substituents such as hydrogen, hydroxy, halogen, carboxyl, cyano, nitro, oxo (═O), thio (═S), substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted Alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted arylalkenyl Substituted, unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted amino, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted heterocycloalkyl ring, substituted or unsubstituted heteroarylalkyl , Substituted or unsubstituted heterocyclic ring, substituted or unsubstituted guanidine, -COORx, -C (O) Rx, -C (S) Rx, -C (O) NRxRy, -C (O) ONRxRy, -NRxCONRyRz, -N (Rx) SORy, -N ( Rx) SO 2 Ry, - (= N-N (Rx) Ry), - NRxC (O) ORy, -NRxRy, -NRxC (O) Ry -, - NRxC (S ) Ry-NRxC (S) NRyRz , -SONRxRy -, - SO 2 NRxRy, -ORx, -ORxC O) NRyRz, -ORxC (O) ORy-, -OC (O) Rx, -OC (O) NRxRy, -RxNRyC (O) Rz, -RxORy, -RxC (O) ORy, -RxC (O) NRyRz, -RxC (O) Rx, -RxOC ( O) Ry, -SRx, can include -SORx, -SO ₂ Rx, the -ONO _2, wherein, Rx in each group of the above, Ry and Rz are May be the same or different and may be a hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted Substituted arylalkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted amino, substituted or Unsubstituted aryl, substituted or unsubstituted heteroaryl, "substituted heterocycloalkyl ring" in substituted or unsubstituted heteroarylalkyl, or include a substituted or unsubstituted heterocyclic ring.

The above silicone materials are merely exemplary and can benefit from being stored in a solution containing an anionic polymer according to the present invention, disclosed in various literature, contact lenses and other Other materials for use as cationic substrates that are continuously being developed for use in medical devices can also be used. For example, other suitable cationic monomer materials have a molecular weight of about 600 g / mol or less and can be protonated at a pH value (physiological pH value) of about 7.2 to about 7.4. Or a quaternary ammonium group. Illustrative of the monomers, tertiary C ₁ -C ₁₀ alkyl acrylic acid and methacrylic acid, C ₂ -C ₃ alkanol and benzyl aminoethyl or N- morpholinoethyl ester, for example, 2-dimethylaminoethyl methacrylate (DMEAM), 2-N-morpholinoethyl methacrylate (MEM), N, N-diethanolaminoethyl methacrylate, N, N-dimethoxyethylaminoethyl methacrylate, vinylamine, aminostyrene, 2-vinylpyridine, 4-vinylpyridine, N- (2- Vinyloxyethyl) piperidine and quaternary ammonium compounds such as 3-trimethylammonium-2-hydroxypropyl methacrylate chloride (TMAHPM), 2-trimethylammonium ethyl methacryl hydroxide, - trimethylammonium ethyl acrylate hydroxide, 2-trimethyl ammonium methyl methacrylate chloride, 2-trimethyl ammonium methyl acrylate chloride, and, and a 2-methacryloyloxyethyl trimethyl ammonium methyl sulfate.

  Silicone-containing monomers will be added to the monomer mixture in smaller amounts, for example, up to about 15% by weight, based on the total weight of the monomer mixture. Generally, the silicone-containing monomer is present in an amount ranging from about 0.1 to about 15 weight percent, based on the total weight of the monomer mixture.

  The silicone hydrogels of the present invention typically polymerize a monomer mixture containing at least a higher amount of non-silicone-containing monomer and at least a lower amount of silicone-containing monomer using conventional polymerization conditions well known to those skilled in the art. For example, by exposing the monomer mixture to light irradiation such as visible light or UV radiation, heat or both to induce polymerization. In general, the polymerization can be conducted, for example, under an inert atmosphere of nitrogen or argon for about 15 minutes to about 72 hours. If desired, the resulting polymerization product can be dried under vacuum, eg, for about 5 to about 72 hours, or placed in an aqueous solution prior to use.

  A polymerization initiator can be included in the monomer mixture to facilitate the polymerization process. Typical radical thermal polymerization initiators are organic peroxides such as acetal peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, tertiary butyl peroxypivalate, peroxydicarbonate and the like and mixtures thereof. Exemplary UV initiators are those known in the art, such as benzoin methyl ether, benzoin ethyl ether, Darocure 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) and Irgacure ( Irgacure) 651 and 184 (Ciba-Geigy) etc. and mixtures thereof. Generally, the initiator will be used in the monomer mixture at a concentration of about 0.1 to about 5% by weight of the total amount of mixture.

  The polymerization of the monomer mixture is generally performed in the presence of a diluent. The diluent is generally removed after polymerization and replaced with water in extraction and hydration procedures well known to those skilled in the art. Typical diluents include diols, alcohols, alcohol / water mixtures, ethylene glycol, glycerin, liquid polyethylene glycols, low molecular weight linear polyhydroxyethyl methacrylate, glycolic esters of lactic acid, formamide, ketones, dialkyl sulfoxides, butyl carbitol, etc. And mixtures thereof.

  Polymerization can also be carried out in the absence of diluent to form a xerogel. The xelgel can then be hydrated to form a hydrogel, as is well known in the art.

  The monomer mixture can further comprise a hydrophobic monomer. Suitable hydrophobic monomers include ethylenically unsaturated hydrophobic monomers such as (meth) acrylate containing hydrophobic monomers, N-alkyl (meth) acrylamide containing hydrophobic monomers, vinyl carbonate containing hydrophobic monomers, vinyl carbamate containing hydrophobic monomers. Monomer, fluoroalkyl (meth) acrylate-containing hydrophobic monomer, N-fluoroalkyl (meth) acrylamide-containing hydrophobic monomer, N-fluoroalkylvinylcarbonate-containing hydrophobic monomer, N-fluoroalkylvinylcarbamate-containing hydrophobic monomer, styrene And a hydrophobic monomer containing polyoxypropylene (meth) acrylate and a mixture thereof.

In a preferred embodiment, the hydrophobic monomer is represented by the following formula XXV.

In the above formula, R ₃₀ is methyl or hydrogen, R ₃₁ is —O— or —NH—, and R ₃₂ and R ₃₄ are independently a group consisting of —CH ₂ —, —CHOH— and —CHR ₃₅ —. R ₃₄ and R ₃₅ are independently branched C ₃ -C ₈ alkyl groups, n is an integer of at least 1, and m and p are independently 0 or at least 1. An integer, where the sum of m, p and n is 2, 3, 4 or 5. Representative examples of hydrophobic monomers include, but are not limited to, 4-t-butyl-2-hydroxycyclohexyl methacrylate (TBE), 4-t-butyl-2-hydroxycyclopentyl methacrylate, 4-t-butyl. Examples include 2-hydroxycyclohexyl methacrylamide (TBA), 6-isopentyl-3-hydroxycyclohexyl methacrylate, and 2-isohexyl-5-hydroxycyclopentyl methacrylamide. Preferred hydrophobic monomers include TBE and TBA.

  The hydrophobic monomer will usually be present in the monomer mixture in an amount ranging from 0 to about 15% by weight, based on the total weight of the monomer mixture.

  The monomer mixture can also contain a crosslinking agent. However, usually either the non-silicone-containing hydrophilic monomer or the silicone-containing monomer functions as a cross-linking agent (the cross-linking agent is defined as a monomer having a polyvalent polymerizable functionality) or a separate cross-linking agent is used. May be. Cross-linking agents are known in the art, and typical cross-linking agents include allyl methacrylate and ethylene glycol dimethacrylate (EGDMA). For other acrylic-containing, vinyl-containing and / or styrene-containing hydrophobic monomers, crosslinkers such as methacryloxyethyl vinyl carbonate (HEMAVC), 4-vinylphenyl vinyl carbonate and 4-vinylphenyl carbamate are used.

  The monomer mixture may also include a reinforcing monomer. The term “strengthening monomer”, as used herein, relates to a monomer that can be polymerized with a hydrophilic monomer to provide a polymeric material with improved physical properties, particularly tear and tensile strength. It is understood that the additional hydrophilic monomer is defined as different from or excluding the reinforcing monomer. The reinforcing monomer will usually be present in the monomer mixture in an amount ranging from about 0.01 to about 20% by weight, preferably from about 5 to about 10% by weight, based on the total weight of the monomer mixture.

  The monomer mixture may include a colorant defined as an agent that imparts some color to the lens when incorporated into the final lens. Conventional colorants are known in the art, and colorants include non-polymerizable drugs or polymerizable drugs containing activated unsaturated groups that are reactive with lens-forming monomers. One preferred example of this latter class of compounds is the compound 1,4-bis (4- (2-methacryloxyethyl) phenylamino) anthraquinone, which is disclosed in US Pat. No. 4,997,897. Blue visible colorant.

  The hydrogel material of the present invention has a moisture content greater than 50%. In one embodiment, the high water content hydrogel material of the present invention will have a water content of at least about 70% water. In another embodiment, the high water content hydrogel material of the present invention will have a water content of at least about 80% water. The high water content silicone hydrogel of the present invention can have an oxygen permeability coefficient of about 30 bar to about 70 bar, preferably about 40 bar to about 60 bar. It is also preferred that the hydrogel material has a water contact angle of less than about 90 degrees.

  According to various preferred embodiments, the hydrogel material is suitable for biomedical applications. The term “molded article for use in biomedical applications” or “biomedical device or material” refers to a physics that makes the hydrogel material disclosed herein suitable for long-term contact with living tissue, blood and mucous membranes. It means having chemical properties.

  In general, contact lenses can be obtained by loading the monomer mixture into a mold and then subjecting it to light irradiation or heat to cure the monomer mixture in the mold. Various methods are known for curing monomer mixtures in the manufacture of contact lenses, including spin casting and static casting. The spin casting method involves loading a monomer mixture into a mold and spinning the mold in a controlled manner while exposing the monomer mixture to light. In the static casting method, one mold section is shaped to form the front lens surface, and the other mold section is shaped to form the back lens surface. Curing the monomer mixture by exposure to. Such methods are described in U.S. Pat. Nos. 3,408,429, 3,660,545, 4,113,224, 4,197,266, and No. 5,271,875. Furthermore, the monomer mixture may be cast in the form of a rod or button and then lathe cut to the desired lens shape.

  The following examples are provided to enable one of ordinary skill in the art to practice the invention and are merely exemplary of the invention. The examples should not be read as limiting the scope of the invention as defined in the claims.

Analytical Measurements Modulus of elasticity can be measured using an Instron (Model 4502) instrument according to ASTM D-1708a, where a hydrogel copolymer film sample is immersed in an aqueous borate buffer solution. A suitable size for the film sample is a gauge length of 22 mm and a width of 4.75 mm, and the sample is further formed at both ends forming a dogbone shape for gripping the sample by clamping an Instron instrument. And has a thickness of 100 ± 50 micrometers.

  The moisture content of the hydrated film was measured by gravimetric analysis. Two sets of fully hydrated lenses containing 5 lenses per set are removed from the storage device. Absorb the lens with filter paper to remove residual surface water. Each set is then weighed individually to determine the “wet mass”. The two sets of lenses are then placed in a 500-650 watt microwave oven at high settings for 10 minutes. The two sets of lenses are then removed from the microwave oven and each set is weighed individually to determine the “dry mass”. The% moisture content of each set is determined using the following equation: The moisture content reported represents the average of the two sets.

The oxygen transmission coefficient (also called Dk) was determined by the following procedure. Other methods and / or equipment may be used as long as the oxygen permeability coefficient value obtained is similar to the above method. Using an O ₂ Permeometer model 201T (Createch, Albany, California USA) with a probe comprising a central circular gold cathode at the probe end and a silver anode insulated from the cathode, the polarographic method (ANSI Z80. 20-1998) to measure the oxygen permeability coefficient of silicone hydrogels. Measurements are made on pre-tested pinhole-free flat silicone hydrogel film samples having three different center thicknesses of 150-600 micrometers. The center thickness of the film sample can be measured using a radar (Rehder) ET-1 electronic thickness meter.

  Generally, the film sample has the shape of a circular disc. Measurements are made with probes and film samples immersed in a bath containing circulating phosphate buffer solution (PBS) equilibrated at 35 ° C. + / − 0.2 °. Prior to immersing the probe and film sample in the PBS bath, center the film sample on the cathode pre-wetted with equilibrated PBS, ensuring air bubbles or excess PBS between the cathode and film sample. The film sample is then secured to the probe by a mounting cap so that it is not present and then the cathode portion of the probe contacts only the film sample. In silicone hydrogel films, it is often useful to use, for example, a Teflon polymer film having a circular disc shape between the probe cathode and the film sample. In such a case, a Teflon membrane is first placed on the pre-moistened cathode, after which there are no bubbles or excess PBS under the Teflon membrane or film sample. In this way, a film sample is placed on the Teflon membrane. Once the measurements are collected, only data with a correlation coefficient value (R2) greater than 0.97 should be entered into the Dk value calculation.

  At least two Dk measurements and R2 fit values are obtained per thickness. Using a known regression analysis, the oxygen transmission coefficient (Dk) is calculated from film samples having at least three different thicknesses. Film samples hydrated with solutions other than PBS are first soaked in pure water and allowed to equilibrate for at least 24 hours, then soaked in PHB and allowed to equilibrate for at least 12 hours. The instrument is periodically cleaned and periodically calibrated using RGP standards. +/− of literature values defined by William J. Benjamin et al., The Oxygen Permeability of Reference Materials, Optom Vis Sci 7 (12s): 95 (1997), the entire disclosure of which is incorporated herein by reference. The upper and lower limits are determined by calculating 8.8%.

Material name Literature value Lower limit Upper limit Fluoroperm 30 26.2 24 29
Menicon EX 62.4 56 66
Quantum II 92.9 85 101

Example 1
A base formulation containing N-vinyl-2-pyrrolidone (NVP) (90% by weight) and 4-t-butyl-2-hydroxycyclohexyl methacrylate (TBE) (10% by weight) was prepared. To this formulation, ethylene glycol dimethacrylate (EGDMA) (0.15 wt%), 2-hydroxyethyl methacrylate (HEMA) vinyl carbonate (0.15 wt%) and a cationic having the general structure defined by Formula VII Silicone-based trismethacrylate (5% by weight) as well as Vazo® 64 (azobisisobutyronitrile) (AIBN)) (0.5% by weight) were added. The resulting mixture was heat cured for about 3 hours. The resulting film had an elastic modulus of 40 g / mm ² , a moisture content of 83%, and a Dk of 51 barrer.

Example 2
A base formulation containing NVP (90% by weight) and TBE (10% by weight) was prepared. To this formulation was added HEMA vinyl carbonate (0.30% by weight), silicone based methacrylate (15% by weight) and AIBN (0.5% by weight). The resulting monomer mixture was heat cured for about 3 hours. The resulting film had an elastic modulus of 52 g / mm ² , a moisture content of 79%, and a Dk of 42 barrer. The silicone-based methacrylate used in this example has the following formula:

Example 3
A base formulation containing NVP (90% by weight) and TBE (5% by weight) was prepared. To this formulation, allyl methacrylate (0.38% by weight), ethylene glycol dimethacrylate (EGDMA) (0.38% by weight), tris (trimethoxysilylpropyl) methacrylate (TRIS-MA) (5% by weight) and AIBN ( 0.5% by weight) was added. The resulting monomer mixture was heat cured for about 3 hours. The resulting lens had an elastic modulus of about 50 g / mm ² , a moisture content of about 78%, and a Dk of about 42 barrer.

Example 4
A base formulation containing NVP (90% by weight) and TBE (10% by weight) was prepared. To this formulation, allyl methacrylate (0.20% by mass), ethylene glycol dimethacrylate (EGDMA) (0.20% by mass), tris (trimethoxysilylpropyl) methacrylate (TRIS-MA) (5% by mass) and AIBN ( 0.5% by weight) was added. The resulting monomer mixture was heat cured for about 3 hours. The resulting lens had an elastic modulus of about 80 g / mm ² , a moisture content of about 79%, and a Dk of about 45 barrer.

Example 5
A base formulation containing NVP (90% by weight) and TBE (10% by weight) was prepared. To this formulation, allyl methacrylate (0.38% by weight), ethylene glycol dimethacrylate (EGDMA) (0.38% by weight), monomethacryloxypropyl terminated polydimethylsiloxane (5% by weight) and AIBN (0.5% by weight). ) Was added. The resulting monomer mixture was heat cured for about 3 hours.

  It will be understood that various changes may be made to the embodiments disclosed herein. Therefore, the above description should not be construed as limiting, but merely as exemplifications of preferred embodiments. For example, the functions described above and implemented as the best mode for operating the present invention are for illustrative purposes only. Other embodiments and methods may be practiced by those skilled in the art without departing from the spirit and scope of the invention. Moreover, those skilled in the art will envision other modifications within the scope and spirit of the features and advantages appended hereto.

Claims (26)

  A silicone hydrogel formed from a hydrated polymerization product of a monomer mixture comprising (a) a greater amount of non-silicone-containing hydrophilic monomer and (b) a smaller amount of silicone-containing monomer, the moisture content exceeding 50% by weight.   The silicone hydrogel of claim 1, wherein the moisture content is greater than about 70% by weight.   The silicone hydrogel of claim 1, wherein the moisture content is greater than about 80% by weight.   The silicone hydrogel of claim 1, wherein the oxygen permeability coefficient is from about 30 to about 70 barrer.   The silicone hydrogel of claim 1, wherein the oxygen permeability coefficient is from about 40 to about 60 barrer. The silicone hydrogel of claim 1, having a moisture content greater than about 70% by weight, an oxygen permeability coefficient of about 40 to about 60 barrer, and an elastic modulus of about 20 g / m ² to about 120 g / m ² . The silicone hydrogel of claim 1, having a moisture content greater than about 80% by weight, an oxygen permeability coefficient of about 40 to about 60 barrer, and an elastic modulus of about 20 g / m ² to about 120 g / m ² .   The non-silicone-containing hydrophilic monomer is N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate, N- (2-hydroxyethyl) methacrylamide, glyceryl methacrylate, N-methacryloylglycine, (2 The silicone hydrogel of claim 1 selected from the group consisting of -hydroxy-3-methacryloylpropyl) -4-methoxyphenyl ether and mixtures thereof.   The silicone hydrogel of claim 1, wherein the non-silicone-containing hydrophilic monomer is present in the monomer mixture in an amount greater than about 65% by weight.   The silicone hydrogel of claim 1, wherein the non-silicone-containing hydrophilic monomer is present in the monomer mixture in an amount greater than about 80% by weight.   The silicone hydrogel of claim 1, wherein the silicone-containing monomer is a tris (trialkylsiloxy) silylalkyl methacrylate-containing monomer.   The silicone hydrogel of claim 1, wherein the silicone-containing monomer is a tris (trimethylsiloxy) silylpropyl methacrylate-containing monomer.   The silicone hydrogel of claim 1, wherein the silicone-containing monomer is present in the monomer mixture in an amount less than about 15% by weight.   A contact lens produced from the polymerization product of a monomer mixture comprising (a) a larger amount of non-silicone-containing hydrophilic monomer and (b) a smaller amount of silicone-containing monomer, the contact lens having a water content of 50% by weight. Contact lenses composed of more than a silicone hydrogel.   The contact lens of claim 14, wherein the moisture content is greater than about 70% by weight.   The contact lens of claim 14, wherein the moisture content is greater than about 80% by weight.   The contact lens of claim 14, wherein the oxygen transmission coefficient is from about 30 to about 70 barrer. Water content greater than about 70 wt%, the oxygen permeability coefficient is about 40 to about 60 Barrers, and an elastic modulus of about 20 g / m ² ~ about 120 g / m ^2, according to claim 14, wherein the contact lens. Water content greater than about 80 wt%, the oxygen permeability coefficient is about 40 to about 60 Barrers, and an elastic modulus of about 20 g / m ² ~ about 120 g / m ^2, according to claim 14, wherein the contact lens.   The non-silicone-containing hydrophilic monomer is N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate, N- (2-hydroxyethyl) methacrylamide, glyceryl methacrylate, N-methacryloylglycine, (2 15. A contact lens according to claim 14, selected from the group consisting of -hydroxy-3-methacryloylpropyl) -4-methoxyphenyl ether and mixtures thereof.   The contact lens of claim 14, wherein the non-silicone-containing hydrophilic monomer is present in the monomer mixture in an amount greater than about 65% by weight.   A silicone hydrogel formed from a hydrated polymerization product of a monomer mixture comprising (a) a non-silicone-containing hydrophilic monomer of greater than about 65% by weight and (b) a silicone-containing monomer of less than about 15% by weight, wherein the moisture content is Silicone hydrogels having greater than 50% by weight, an advancing contact angle of about 100 degrees or less, and an oxygen permeability coefficient of about 30 bar to about 70 bar.   The non-silicone-containing hydrophilic monomer is N, N-dimethylacrylamide, N-vinyl-2-pyrrolidone, 2-hydroxyethyl methacrylate, N- (2-hydroxyethyl) methacrylamide, glyceryl methacrylate, N-methacryloylglycine, (2 23. A silicone hydrogel according to claim 22, selected from the group consisting of -hydroxy-3-methacryloylpropyl) -4-methoxyphenyl ether and mixtures thereof.   23. The silicone hydrogel of claim 22, wherein the moisture content is greater than about 70% by weight and the oxygen permeability coefficient is from about 40 to about 60 barrer.   About 90% by weight N-vinyl-2-pyrrolidone, about 5-10% by weight 4-tert-butyl-2-hydroxycyclohexyl methacrylate, about 0.20-0.38% by weight allyl methacrylate, about 0.20 Silicone hydrogel formed from a hydrated polymerization product of a monomer mixture comprising ˜0.38 wt% ethylene glycol dimethacrylate, about 5 wt% silicone-containing monomer and about 0.5 wt% azobisisobutyronitrile A silicone hydrogel having a water content of more than 50% by mass.   26. The silicone hydrogel of claim 25, wherein the silicone-containing monomer is selected from the group consisting of tris (trimethoxysilylpropyl methacrylate) and monomethacryloxypropyl terminated polydimethylsiloxane.